Refractory and method of making



Patented Aug. 30, 1949 METHOD OF 3W i e Q cg: Q West-i iter iii-Puri Cambridge, Mass assignor to 'ompany',.IRiclimond, Ya,v 9.,

Application December 1945',"-

- semi-No. 634,145.

lgciaims (Cl. 1065-63.)

This invention relates to refractories-:andshas for its objectthe proiiisionaonan impmued refractory and a methodvofrpredncing the refractory. The invention-is esneciallyeoricei ned with refractories forusain.iiningifiirnacesspots, ladies, cells and-other vessels forsaltefusions onsimilarmolten masses, .and provides an impi oiied refractory ccmprising aluminum; nitridiit'ogether wviitirebinding material. Thelinyentiompmvidesvessels for-the treatment. on produetioro.o'fa,aluminium the.-interior surface of whfclit-is a remactory formedlargeiyof aluminmn-snitrides While the-irefractories.--. of the invention have severalusesasiinitheiglass mairin industr'm they' are especially advantageous inkthe aiuminumin dustry forlining vessel-s ren aluminifercusfusions, such as. aluminumwredue'tiomccilss ladies; cruelbles, metal refining cells masseuse- Th'e alumtnum nitride refractornsof tiic-binventionsis very tough, has a thigh-melting: point andsis nei-ther attacked nor penetrated to any apprciable ek tenlt byecryolitetfusieiiss The refractory forms an especially important combination with electrically non-conducting refractor yfr'such as fused alu ina-cam raman whieinare cram lite. In one of its embodiments -,the;inyeptien pro vides a refractory cgmposition formed by heating in contact with nitro'genapnlyerulent mixture comprising, as the major a fl ride iaieria sash ansiearbon uch as charcoal. a refractory; cempqsit imrof e i e i n. as usrellrete usssis Seam-mixtures comprises a mixture of particles of aluminum nitride, aluminum oxide, a halide such as cryclite or calcium fluoride, and residual carbon. The aluminum oxide and halide mixture acts as a binder and gives the refractory strength and rigidity. The aluminum nitride makes the aluminum oxide resistant to solution in fused halide baths.

The invention also provides a composite refractory comprising a refractory material with a lining comprising aluminum nitride bonded thereto, for example, a composite refractory comprising fused alumina, fused magnesia or fused aluminamagnesia spinel with a lining or veneer comprising an aluminum nitride refractory. The lining may be bonded by fusion to the refractory or physically attached thereto as by interlocking connections. Where the refractory is formed as moment. aluminum...

2; a. bonded lining or.- veneenitis preierable to form it, over a very dense-brick suciims. electroroast alumina which is as vitreous aspossible...

In. one of. its aspects,,the inyenticn-.proyides a. method ofproducing an aluminu nnitride refrace tory involving the, heating cfvpulverulent num, such as atomized aluniinum. to a-tempera ture around 1000 C. in nitrogen, such as in the atmosphere while protecting the aluminum froiri undue oxidation; I have foundth'at sin-aluminum nitride refractorymay be formed by'heating ery fine aluminum powde-n minus mil-mesh:- wan powdered; charcoal, to saytemneratureibeiem the agglomerating temperature-ref the. aluminumesaw aro nd 10001?- C., in, the. atmosphere and: theta may convert most,. if. not allsotthe aluminum-to; its; nitride. A, certain? amount ofinxmemonzcare ban; dioxide is;avai1 able,andga partmitheaiumie num is; oxidized to: aluminum ,exidee. 11s; such; operations anundueiemountaofsaiuminumzmcida i-sprevented from, form n i-by hesunotectiomafs forded by: the, ,carbomor'; thercarbcnzmonozida formed.: by 1oxidatiomohthacharcoah Thfiflmolib.

lyhavewfqundi it. advantageouseto'euse-gfrem;

10%, 150, 20% ofchaiuzoatarnii'a lsialide one! from 10% to 20% of calcimmfiuoririeserrswsmw' to 20% of cryolite in the composition. When the aluminum nitride refractory composition is for use in the reduction of bauxite solutions in cryolite, as in the Hall process, it is more eflective to use as a halide calcium fluoride because of its higher melting point.

In still another aspect of my invention, I may subject a pulverulent mixture of aluminum, a small amount of alumina, and carbon to a temperature around 1000 C. in an atmosphere of nitrogen and form a mixture of aluminum nitride, aluminum carbide, alumina and carbon. This mixture may be ground with cryolite and fused.

I may form a refractory composition of the invention by mixing and fusing to ether aluminum nitride and binder such as cryoiite or cal-i.

cium fluoride, with or without alumina or carbon. I may also mix and fuse together aluminum nitride, aluminum carbide, cryolite or calcium fluoride and a little carbon if desired. In either of these mixtures in which the aluminum nitride is formed before mixing, I may use from around 60% to 85% of the nitride to form very effective compositions.

One of the advantageous aspects of the invention is that I may form the refractory in the vessel whereitnis to remain for use. For example, in lining an electrolytic reduction cell, such as one with electrically non-conducting fused alumina or magnesia, I may apply a lining of the aluminum, carbon and halide mixture to the alumina or magnesia and fill'the space with coke which is heated as an electrical resistor by passing an electric current therethrough between a pair of electrodes. In, say to 20 hours, a dense, tough and inert refractory lining is formed that is chemically inert to aluminiferous fusions.

In carrying out a method of the invention, I may use aluminum in any suitable state of fineness, say, from 40 to 200 mesh, a very effective size being through 100 mesh. The carbon in the form of charcoal or petroleum cok and the halide, say, calcium fluoride, may be of about the same fineness. The ingredients are mixed together dry and then rammed in place, as a lining between bricks and a core or into molds. In one example, the following materials were used in formin the composition:

- A dry mixture of the material was rammed between fused dense vitreous alumina bricks of a cell and a plywood form. The space inside the plywood form was filled with pea-sized coke and heated electrically as a resistor to a temperature of around 1100 C. In five hours the baking was complete and the coke was removed. Since the material undergoes an appreciable expansion which is not easily determined, it is advisable to make the lining thicker than required and chisel it down to the desired thickness While red hot. Moreover, the exterior is apt to be high in alumina, when the lining is formed as above 'described, which should be removed. The above lining comprised about 70% aluminum nitride, residual aluminum, cryolite and some carbon, and was impervious to the cryolite bath. One characteristic of the lining is that vessels lined with it may be used for cryolite fusions before the nitriding is complete. The soaking in cryolite makes the lining hard and tough and the nitriding continues during use.

In another example the following composition was used:

Per cent Alumina powder 99% pure (-100 mesh) 86 Fluorspar 6 Cryolite 4 Charcoal (-60 mesh) 4 containing from about 60% to 85% of aluminum nitride, from about 10% to 20% of a binder selected from the group consisting of calcium fluoride and cryolite, with the remainder consisting of carbon and aluminiferous material selected from the group consisting of aluminum oxide, aluminum carbide and aluminum.

2. A refractory as set forth in claim 1 in which the binder is calcium fluoride.

3. A refractory as set forth in claim 1 in which the binder is cryolite.

4. A refractory as set forth in claim 1 in which the carbon does not exceed 5%.

5. The method of producing a fused refractory containing aluminum nitride which comprises forming a mixture consisting of pulverulent aluminum, from about 10% to 20% of carbon and from about 10% to 20% of a binder material selected from the group consisting of calcium fluoride and cryolite, heating the admixture at an elevated temperature around 1000 C. in an atmosphere containing nitrogen to convert the aluminum largely to aluminum nitride, and continuing such heating until the admixture contains about to aluminum nitride.

6. The method of producing a fused refractory as set forth in claim 5 in which the binder material is calcium fluoride.

7. The method of producing a fused refractory as set forth in claim 5 in which the binder material is cryolite.

ARTHUR F. JOHNSON.

REFERENCES CITED The following references are of record in the file of this patent:

FOREIGN PATENTS Number Country Date 1,961 Great Britain 1912 242,455 Germany 1912 438,998 France 1912 

